2-cyclobuten-1-one compounds and process for their preparation



United States Patent 3,408,398 Z-CYCLOBUTEN-l-ONE COMPOUNDS AND PROCESSFOR THEIR PREPARATION James C. Martin, Kingsport, Tenn., assignor toEastman Kodak Company, Rochester, N.Y., a corporation of New Jersey NoDrawing. Filed Mar. 17, 1964, Ser. No. 352,629 11 Claims. (Cl. 260-586)ABSTRACT OF THE DISCLOSURE 2-cyclobuten-l-yne compounds are prepared bycombining ketenes and 1-butene-3-yne compounds. The reaction of dimethylketene and l-methoxy-l-butene-B-yne to produce4,4-dimethyl-3-(Z-methoxyvinyl)-cyclobuten l-one is representative. Thenovel Z-cycIobuten-l-one compounds are eflfective plasticizers forresins such as polyvinyl chloride.

This invention relates to novel chemical compounds and to theirpreparation. More particularly, it relates to novel Z-cyclobuten-l-onecompounds and to novel methods for preparing them.

The novel 2-cyclobuten-1-one compounds have the formula:

I. HCC=O R2oCH=oHii- R in wherein R and R each represents a memberselected from the group consisting of hydrogen, an alkyl radical and anaryl radical and wherein R and R together with the carbon atom to whichthey are attached represents a member selected from the group consistingof cyclopentylidene and cyclohexylidene and R represents a memberselected from the group consisting of an alkyl radical, a cycloalkylradical and an aryl radical.

In accordance with the process of the invention the novel2-cyclobuten-1-one compounds of the invention are prepared by combininga ketene having the formula:

II. R

with a 1-buten-3-yne compound having the formula:

III. R2OCH=CHCECH wherein R, R and R have the meaning previouslyassigned to them. The novel Z-cyclobuten-l-one product formed can beisolated either by distillation or by crystallization.

The following equation illustrates the process of the invention:

The temperatures employed in carrying out the process of the inventionvary from about 0 C. to about 150 C. The process is ordinarily carriedout by gradually adding the ketene to the l-buten-3-yne compound. Whilethe process is normally carried out using an already prepared ketene, ifdesired, the process can be carried out by forming the ketene in situ.

The process of the invention can be carried out with or without asuitable solvent. However, the use of a solvent is generally preferred.Suitable solvents are materials that serve to dissolve the reagentsinvolved in the Patented Oct. 29, 1968 "ice process but which do notreact with them. Suitable inert solvents include, for example, diethylether, diisopropyl ether, dioxane, tetrahydrofuran, diethylketone,methylisobutylketone, hexane, naphtha, isooctane, benzene, toluene,xylene, carbon tetrachloride, chloroform, tetrachloroethane,acetonitrile, isobutyronitrile, ethyl acetate, butyl acetate, etc., anddipolar aprotic solvents such as dimethyl sulfoxide, dimethyl formamide,ethylene carbonate, sulfolane, etc. The function of the solvent can bequite important because in some cases the use of polar solventsaccelerates the reaction and frequently increases the yield.

When R, R and R are alkyl each typically represented an alkyl radicalhaving 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl,butyl, sec.butyl, tert.butyl, pentyl, hexyl, heptyl, octyl,Z-ethylhexyl, etc. although they can be a higher alkyl radical such asnonyl, decyl, undecyl, dodecyl, tridecyl, pentadecyl and octadecyl, forexample. In general, R, R and R are preferably lower alkyl, tag, of 1 to4 carbon atoms.

Illustrative of the ketenes having the Formula I are ketene,dipropylketene, methylketene, diisopropylketene, ethylketene,ethylbutylketene, propylketene, dibutylketene, isopropylketene,diisobutylketene, butylketene, di tert.butyl) ketene, isobutylketene,dipentylketene, tertiarybutylketene, dihexylketene, pentylketene,diheptylketene, hexylketene, dioctylketene, heptylketene, di(Z-ethylhexyl ketene, octylketene, ethyldodecylketene,Z-ethylhexylke'tene, didodecylketene, nonylketene, dipentadecylketene,decylketene, dihexadecylketene, undecylketene, didodecylketene,dodecylketene, dioctadecylketene, tridecylketene, methylpropylketene,tetradecylketene, isobutylethylketene, pentadecylketene,pentamethyleneketene, hexadecylketene, hexamethyleneketene,heptadecylketene, phenylketene, octadecylketene, p-methylphenylketene,dimethylketene, ethoxyphenylketene, ethylmethylketene,p-ethoxyphenylketene, diethylketene, diphenylketene, andethylpropylketene, di (p-methylphenylketene, ethylisopropylketene, forexample.

Illustrative of the 1-buten-3-ynes used in carrying out the process ofthe invention are 1-rnethoxy-1-buten-3 -yne, 1-ethoxy-1-buten-3-yne,1-propoxy-1-buten-3 -yne, 1-isopropoxy-1-buten-3 -yne,1-butoxy-1-buten-3-yne, 1-pentyloxy-1-buten-3-yne,l-hexyloxy-1-buten-3-yne, 1-heptyloxy-1-buten-3 yne,1-octyloxy-1-buten-3 -yne, l decyloxy-I-buten-3-yne,1-undecyloxy-1-buten-3-yne, l-dodecyloxy-l-buten-3-yne,l-tetradecyloxy-1-buten-3-yne, l-octadecyloxy-1-buten-3-yne,l-cyclohexyloxy-l-buten-3-yne, 1-phenoxy-1-buten-3 -yne,

l- (p-methylphenoxy) -1-buten-3-yne and l-(p-methoxyphenoxy)-1-buten-3-yne, for example.

l-buten-3-yne compounds, such as 1-alkoxy-1-buten-3- yne compounds, forexample, are well known. They can 3 be prepared by the base catalyzedaddition of alcohols to diacetylene, as described by T. Herbertz, Ben,85, 475- 82 (1952) The novel 2-cyclobuten-l-one compounds of theindoublet centered at 5.42 (olefinic ring proton), singlet at 3.85(methoxy group), and a singlet at 1.15 (two methyl groups); trans, adoublet centered at 7.90

vention are useful as plasticizers for cellulose acetate 5 butyrate andpolyvinyl chloride, for example.

The following examples illustrate the invention: a doublet centered at(Olefilllc T1118 P doublet centered at 5.88 Example 1 6 10 (OC= H) asinglet at 3.72 (methoxy group), and a singlet at 1.30 oH, io=o=oCH3OCH=OHCECH (two methyl groups).

H(fi (l3=O Example 2 CHSOOH=CH CCTGH3 A solution of 82 g. (1.0 mole) ofl-methoxy-l-buten- 3-yne in 200 ml. of acetonitrile was stirred at roomtemperature under nitrogen while 126 g. (1.0 mole) of butylethylketenewas added. After the addition was com- A Solution of 123 (15 moles) ofplete, the solution was refluxed for 2 hours. Distillation yne in 300ml. of ether was stirred at room temperature of this solutlon through alomch Packed column gave under nitrogen While 105 g. (1.5 moles) ofdimethylsome unchangad l'methoxy'l'buten'sfme and ketene was added. Thereaction was exothermic but the of P 'f 3 (zo'methoxyvmyl)'z'cyclobuten'temperature was kept at 20-25" C. by a cooling bath. a l 6065 (501%)Distillation of this solution through a 10-inch packed Analysls' calcd'for C13H20O2' Q column gave unchanged l-methoxy-1-buter1-3-yne andFound: 60.5 g. of 4,4-dimethyl-3-(Z-methoxyvinyl) 2 cyclo- Example 3 gig? gg isgg g' b g b i; 7 9 85 parts (by weight) of cellulose acetatebutyrate and Four idz 70.9; H; 8.2. Th e spectrum was con Parts (byweight) of 44'dimethy1 (z'methoxy' tam with the Structure shown vinyl) 2cyclobuten l one were milled together on SIS 5 d 6 55 Th heated rollsfor 4 minutes at 270 F. uslng a Thropp Infrared Spectrum (Sinean' fan 'fe milling machine. The resulting resin is tough, resilient n.m.r.spectrum of this material contained peaks atdh d h l S tributed to cisand trans isomers of 4,4-dimethyl-3-(2- an as goo p yslca Proper 16methoxyvinyl)-2-cyclobuten 1 one: cis, singlet at 6.95 Ex mple 4 50parts (by weight) of polyvinyl chloride and 50 parts (by weight) of4-n-butyl-4-ethyl-3-(Z-methoxyvinyl)-2-cyclobuten-1-one were milledtogether on heated rolls for 4 minutes at 300 F. using a Thropp millingmachine. The resulting resin is tough, resilient and has Smglet at goodphysical properties.

Under the general conditions described in Example 1 l the followingketene and l-buten-3-yne compounds give (OCZCH) the products shown inthe following tabulation.

TABLE 1 Ketene 1-buten-3-yne Product Kctene l-methoxy-l-buten-Bqne3-(Z-methoxyvinyl)-2-cyclobuten-1-one.

D0 1-butoxy-1-buten-3-yne. 3-(2-butoxyvinyl)-2cyelobuten-l-one.0ctylketene do 4-octyl-3-(2-butoxyvinyl)-2cyclobuten-1-one.D1phenylketene l-oetadeeyloxy-l-buten-IZ-yne4,4-diphenyl-3-(2octadecyloxyvinyl)-2-cycl0buten-1-011e. Methylketene.l-ethoxy-l-buten-iiwne 4-methyl-3-(2ethoxyvinyl)-2-cyclobuten-l-0ne.Ethy1ketene 1-prop0xy-1-buten-3-yne4-ethyl-3-(2-propoxyvinyl)-2-eyclobuten-1-one. Butylketenel-octyloxy-l-buten-B-yne.4-buty1-3-(2-0etyloxyvinyl)-2-cyclobuten-1-one. Decylketenel-methoxy-l-buten-S-yne.- 4-deeyl-3-(2-methoxyvinyl)-2-cyelobuten-1-one.Phenylketene... ....do 4-phenyl-3-(2-methoxyvinyl)-2-cyc1obuten-1-one.Dimethylketene 1-ethoxy-1-buten-3-yne-4,4-dimethyl-3-(Z-ethoxyvinyl)-2-cyclobuten-1-one.

D 1-pr0poxy-1-buten3yne 4,4-din1ethyl-3 (2-pr0poxyvinyl)-2-eyc1obuten1-one.

I pentyIoXy-I-buten-3-yne.

4,4-dimethyl-3-(2-butoxyvinyl)-2-cycl0-buten-1-one.

4,4-dimethyl-3-(2-hexy1oxyvinyl)-2eyclobuten-1-0ne.4,4-dimethyl-3-(2-octyloxyvinyl)-2-cycl0buten-1-0ne.

4,4-dimethyl-3- (2-decyloxyvinyl)-2-cyclobuten-1-one.

4,4-dimethyl-3-(2-octadecyloxyvinyl) -2-cyclobuten-l-one.4,4-dimethyl-3-(Z-eyclohexyloxyvinyl)-2-cyelobnten-l-one.

. 4,4-dimethyl-3-(Zphenoxyvinyl)-2-cyclobuten-1-one.

4,4-diethyl-3-(2-methoxyvinyl)-2-cyclobuten-1-one.4,4-diethyl-3(2-isopr0p0xyvinyl)-2-cyclobuten-1-0ne. 4,4-diethyl-3-(Q-pmethylphenoxyvinyl)-2-cyclobuten-1-one.4,4-d1pr0pyl-EL(Z-methoxyvinyl)-2-cycl0buten-1-one.4,4-diisopropyl-3-(2-methoxyvinyl)-2cyclobuten-1-0ne.4,4-dibutyl-3-(2-methoxyvinyl)-2-cyelobuten-1-0ne.

4-butyl-4-ethyl-3-(2-pentyloxyvinyl)-2cyclobuten-l-one.4,4-dihexy1-3-(2-methoxyvinyl)-2-cyclobuten-l-one.4,4-dioctyl-3-(2-methoxyvinyl)-2-cyclobuten-1-one.

4,4-dideeyl-3-(Z-methoxyvinyl)-2-cyelobuten-1-one.

Didodecylketene .do- 4,4did0decyl-3- (Z-methoxyvinyl)-2-cyclobuten-1-one.

D octadecylketene .do-4,4-dioctadecyl-3-(2-methoxyvinyl)-2-cyclobuten-1-one.

Diph enylketene .do 4,4-diphenyl-3-(2-methoxyvinyl) -2-cyclobuten-1-one.

p-Methylph enylketone .do4p-1nethylphenyl-3-(2-mcthoxyvinyl)-2-cyelobuten-1-one.

etenc l-p-metlloxyplienoxy-1-butcn-3-ync. 3-(2-p-1netl10xypho1ioxyvinyl)-2-cycl0butou-1-one.

TABLE 1C0ntinued Ketene l-hut en 3-yne Pro duet Pentamethyleneketene-1-Ineth0xy-1-buten-3-yne Eff-(3:0

(EH30 CH=CHC-G Dol-butoxy-1-buteu-3-yne H (I?CI=O CHZCHQCHQCHZO CH=CHC-CHexamethyleneketena..- 1-methoxy-1-buten-3-yne. H CH)(|3=O H 0 H=CH-C-Cj Do 1-butoxy-1-buten-3-yne HOC=O ll CHQCH CHtCHiO CH=CHCC Theketene compounds employed in the preparation of the novel compounds ofthe invention can be prepared by 30 methods known in the art, forinstance, by methods described in Organic Reactions, John Wiley andSons, Inc., N.Y. (1946), vol. III, chapter 3. The dialkyl ketenereactants can also be prepared by the method described in copendingapplication, Hasek and Elam, Ser. No. 841,- 961, filed Sept. 24, 1959,now Patent No. 3,201,474 and in Hasek and Elam Canadian Patent 618,772.

Although the invention has been described in considerable detail withparticular reference to certain preferred embodiments thereof,variations and modifications can be effected within the spirit and scopeof the invention as described hereinbefore, and as defined in theappended claims.

I claim:

1. A cyclobutenone compound having the formula:

wherein R and R each represents a member selected from the groupconsisting of hydrogen, an alkyl radical containing from 1 to 18 carbonatoms, phenyl, methylphenyl, methoxyphenyl and ethoxyphenyl; and whereinR and R together with the carbon atom to which they are attachedrepresents a member selected from the group consisting ofcyclopentylidene and cyclohexylidene and R represents a member selectedfrom the group consisting of an alkyl radical containing from 1 to 18carbon atoms, cyclohexyl, phenyl, methylphenyl, methoxyphenyl andethoxyphenyl.

2. A cyclobutenone compound according to claim 1 wherein R, R and R eachrepresents an alkyl radical containing from 1 to 18 carbon atoms.

3. A cyclobutenone compound according to claim 1 wherein R and R eachrepresents hydrogen and R represents an alkyl radical containing from 1to 18 carbon atoms.

4. 4,4-dimethyl-3- (Z-methoxyvinyl) -cyclobuten-1-one.

5. 4 n butyl 4 ethyl 3 (2 methoxyvinyl) 2 cyclobuten-l-one.

6. 3-(2-rnethoxyvinyl)-2-cyclobuten1-one.

7. 4-n-0ctyl-3-(Z-n-butoxyvinyl)-2-cyclobuten-l-one.

8. 4,4 diphenyl 3 (2 octadecyloxyvinyl) 2 cyclobuten-l-one.

9. A process for preparing a cyclobutenone compound having the formula:

which comprises reacting a ketene having the formula R-C=C=0 with a1-buten-3-yne compound having the formula:

R OCH=CHCECH under cycloaddition reaction conditions at a temperature offrom about 0 to about C., and wherein in the foregoing formulas, R and Reach represents a member selected from the group consisting of hydrogen,an alkyl radical containing from 1 to 18 carbon atoms, phenyl,methylphenyl, methoxyphenyl, and ethoxyphenyl; and wherein R and Rtogether with the carbon atom to which they are attached represents amember selected from the group consisting of cyclopentylidene andcyclohexylidene and R represents a member selected from the groupconsisting of an alkyl radical containing from 1 to 18 carbon atoms,cyclohexyl, phenyl, methylphenyl, methoxyphenyl and ethoxyphenyl.

10. A process according to claim 9 which comprises reacting a dialkylketene with a l-alkoxy-l-buten-B-yne and recovering a4,4-dialkyl-3-(2-alkoXyvinyl)-2-cyclobuten-l-one product.

11. A process according to claim 9 wherein the process is carried out ina dipolar aprotic solvent medium.

References Cited UNITED STATES PATENTS 3,288,854 11/1966 Martin 260586OTHER REFERENCES Adams et al.: Organic Reactions, vol. 12, p. 35 (1962).

LEON ZITVER, Primary Examiner.

M. JACOB, Assistant Examiner.

Washington, D.C. 20231 UNITED STATES PATENT OFFICE CERTIFICATE OFCORRECTION Patent No. 3,408,398 October 29, 1968 James C. Martin It iscertified that error appears in the above identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 5, line 71, "4. 4,4-Dimethyl-3-(2-methoxyvinyl)cyclobuten-lone.should read 4. 4,4-Dimethyl-3- (2-methoxyvinyl)-2Cyclobuten-l-one.

Signed and sealed this 10th day of March 1970.

(SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Edward M. Fletcher, Jr.

Attesting Officer

